The object of the present invention is an agent for dyeing fibers, particularly keratin fibers (for example human hair), said agent containing an indole derivative and a carbonyl compound, and to a multicomponent kit for dyeing and subsequently decolorizing fibers, said kit containing both an agent for producing a coloration on the fibers and an agent for the reductive removal of the coloration.
Depending on the starting color of the hair to be dyed and the desired end result, hair colorants fall mainly into the domain of oxidative hair dyes and tinting agents. Oxidative dyes lend themselves eminently to the covering of large gray areas. The oxidative dyes used when the gray area amounts to up to 50% are usually referred to as oxidative tinting agents, whereas the oxidative dyes used when the gray area exceeds 50% or the dyes used for xe2x80x9cbright coloringxe2x80x9d are usually referred to as oxidative dyes. Direct dyes are contained mainly in non-oxidative colorants (tinting agents). Some direct dyes, for example the nitro dyes, can, because of their small size, penetrate into the hair andxe2x80x94at least in the outer regionsxe2x80x94bring about direct dyeing. Such tinting agents are very gentle to the hair, they can usually withstand 6 to 8 hair washings and they allow a gray coverage of about 20%.
In general, direct dyes and oxidative tints are washed out of the hair after a few hair washings. Their durability depends among other things on the hair structure and the color shade used. Oxidative dyes can fade somewhat with time, but as a rule remain on the hair until the next haircut. When it is desired to wear a particular color only for a certain length of time or if the user dislikes a color, however, it may be desirable to be able to remove the hair coloring at any time. Also, when a person""s hair is dyed for the first time, a gentle and complete removal of the coloration can reduce the fear of an excessively drastic color change (xe2x80x9ctest dyeingxe2x80x9d).
European Patent EP 0 847 749 discloses a combination of diiminoisoindoline or 3-aminoisoindolone derivatives and compounds with primary or secondary amino groups for coloring keratin fibers without the addition of an oxidant. It is also known from German Unexamined Patent Application DE-OS 43 35 623 to use for the dyeing of keratin fibers a combination of indolinone derivatives and compounds with primary or secondary amino groups, heterocycles or aromatic hydroxy compounds. Moreover, DE-OS 44 09 143 describes the use of isatin derivatives for the dyeing of keratin fibers. DE-OS 197 45 292 discloses the use of a combination of malonaldehyde derivatives, for example malonaldehyde-bis-dialkyl acetals, and amines or CH-acidic compounds for dyeing hair without the addition of oxidants. Also, DE-OS 197 17 280 discloses the use of a combination of certain heterocyclic aldehydes and amines or CH-acidic compounds for dyeing hair without the addition of oxidants.
A great demand, however, continues to exist for colorants which under mild conditions give intense as well as gentle colorations in a wide range of shades and whichxe2x80x94if desiredxe2x80x94can subsequently be removed at any time.
The object of the present invention is therefore to provide a dyeing system which without the addition of an oxidant (for example hydrogen peroxide) gives a gentle, intense coloration on fibers in the yellow, brown, green and purple range with good fastness properties (light fastness, wash fastness, abrasion resistance) and at the same time permits gentle and complete removal of said coloration at any point in time.
Surprisingly, we have now found that dyes containing an indoline derivative of formula (I) or a 3H-indolium derivative of formula (Ia) as well as a carbonyl compound give in gentle manner intense colorations which can be removed completely at any desired subsequent point in time.
Hence, the object of the present invention is an agent for dyeing fibers, for example wool, silk, cotton or hair, and particularly keratinic fibers, for example human hair, said agent being obtained by mixing two componentsxe2x80x94if necessary with addition of an alkalinizing agent or an acidxe2x80x94and being characterized in that one component (component A2) contains at least one carbonyl compound, particularly an aromatic aldehyde compound, and the other component (component A1) contains at least one indoline derivative of formula (I) or a 3H-indolium derivative of formula (Ia) 
the R1 to R8 and Axe2x88x92 groups in formulas (I) and (Ia) having the following meaning:
R1 denotes a straight-chain or branched C1-C8 alkyl group, C1-C8 monohydroxyalkyl group, C2-C8 polyhydroxyalkyl group, C1-C8 alkoxy-(C1-C8)-alkyl group or a thio-(C1-C8)-alkyl group, a xe2x80x94(CH2)mxe2x80x94Xxe2x80x94(CH2)nxe2x80x94Yxe2x80x94(CH2)pxe2x80x94Ra group, a xe2x80x94(CH2)nxe2x80x94Xxe2x80x94Ra group, a xe2x80x94(CH2)mxe2x80x94Yxe2x80x94(CH2)nxe2x80x94Xxe2x80x94(CH2)pxe2x80x94Ra group, a xe2x80x94(CH2)mxe2x80x94COxe2x80x94(CH2)pxe2x80x94Xxe2x80x94Ra group, a xe2x80x94(CH2)pxe2x80x94Ra group, a xe2x80x94(CH2)mxe2x80x94Xxe2x80x94(CH2)pxe2x80x94COxe2x80x94Yxe2x80x94Ra group or 
xe2x80x83wherein
X and Y independently of each other denote an oxygen atom, a sulfur atom or an NRb group, Ra and Rb independently of each other denote a hydrogen atom, an, optionally substituted, aromatic carbocycle or heterocycle or a straight-chain or branched C1-C8 alkyl group, m and n independently of each other denote an integer from 1 to 6 and p denotes an integer from 0 to 6;
R2 is a hydrogen atom or a straight-chain C1 to C6-alkyl group,
R3 and R4 independently of each other denote a straight-chain or branched C1-C4-alkyl group (particularly a methyl group), a (CH2)nxe2x80x94Rc group, a xe2x80x94(CH2)mxe2x80x94CHRcxe2x80x94Xxe2x80x94(CH2)nxe2x80x94Rc group, a xe2x80x94(CH2)nxe2x80x94COxe2x80x94Rc group, a xe2x80x94(CH2)nxe2x80x94COxe2x80x94XRc group, a (CH2)nxe2x80x94CN group, a xe2x80x94(CH2)nxe2x80x94CHxe2x95x90C(CH3)2 group, a xe2x80x94(CH2)mxe2x80x94Xxe2x80x94CHRcxe2x80x94(CH2)nxe2x80x94Rc group or a xe2x80x94(CH2)nCHxe2x95x90CH group, X standing for an oxygen atom, a sulfur atom or an NRb group, m and n independently of each other denoting 1 to 6 and Rc standing for a hydrogen atom, an, optionally substituted, aromatic carbocycle or heterocycle or a straight-chain or branched C1-C6-alkyl group, providing that the R3 and R4 groups, together, linked through a (CH2)n group (with n=1-3) can also form a spiro compound with the 3H carbon;
R5, R6, R7 and R8 independently of each other denote a straight-chain or branched C1-C4-alkyl group or a C1-C4-hydroxyalkyl group, a hydroxyl group, a methoxy group, a benzyl group, a halogen atom (F, Cl, Br, I), a nitro group, a nitroso group, a cyano group, a trifluoromethyl group, a xe2x80x94CHO group, a xe2x80x94CORd group, a xe2x80x94COOH group, a xe2x80x94CO2Rd group, an xe2x80x94OCORd group, an xe2x80x94OCH2-aryl group, an xe2x80x94SO2NH2 group, an xe2x80x94NH2 group, an xe2x80x94NH3+ group, an xe2x80x94NHRd group, an xe2x80x94NH2Rd+ group, an xe2x80x94N(Rd)2 group, an xe2x80x94N(Rd)3+ group, an xe2x80x94NHCORd group, an xe2x80x94NHCOORd group, a xe2x80x94CH2NH2 group, a xe2x80x94CH2NHRd group, a xe2x80x94CH2N(Rd)2 group, a xe2x80x94CO2CF3 group, a xe2x80x94PO(ORd)2 group, xe2x80x94SO2CHF2 group, an xe2x80x94SO2CF3 group an xe2x80x94SO2Rd group or an xe2x80x94SRd group, wherein Rd denotes a hydrogen atom, an, optionally substituted, aromatic carbocycle or a heterocycle or a C1-C6-alkyl group, providing that at least one of the R5 to R8 groups is different from hydrogen; and
Axe2x88x92 denotes an anion of an organic or inorganic acid.
Axe2x88x92 is preferably a chloride, bromide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenylborate, formate, acetate or propionate ion. The chloride ion, tetrafluoroborate ion, acetate ion and hydrogen sulfate ion are particularly preferred.
Among the compounds of formulas (I) and (Ia), the following are preferred:
1,3,3,4-tetramethyl-2-methyleneindoline and the salts thereof,
1,3,3,5-tetramethyl-2-methyleneindoline and the salts thereof,
1,3,3,6-tetramethyl-2-methyleneindoline and the salts thereof,
1,3,3,7-tetramethyl-2-methyleneindoline and the salts thereof,
1,3,3,6,7-pentamethyl-2-methyleneindoline and the salts thereof,
1,3,3,5,7-pentamethyl-2-methyleneindoline and the salts thereof,
1,3,3,4,7-pentamethyl-2-methyleneindoline and the salts thereof,
5-fluoro-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-isopropyl-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-methoxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-nitro-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-amino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
6-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
6-methoxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-methoxy-6-nitro-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-methoxy-6-amino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5,6-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5,6-dimethoxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5,6-methylenedioxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
4,5-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5,7-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-amino-6-methoxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-amino-7-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-hydroxy-7-amino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,
1-methyl-3-spirocyclopropyl-2-methyleneindoline and the salts thereof,
1-methyl-3-spirocyclohexyl-2-methyleneindoline and the salts thereof,
1-methyl-3-spirocyclohexyl-5-hydroxy-2-methyleneindoline and the salts thereof,
1-methyl-3-spirocyclohexyl-5-methoxy-2-methyleneindoline and the salts thereof,
the following being particularly preferred:
1,2,3,3,5-pentamethyl-3H-indolium iodide,
1,2,3,3,7-pentamethyl-3H-indolium tetrafluoroborate,
1,2,3,3,6,7-hexamethyl-3H-indolium tetrafluoroborate,
1,2,3,3,5,7-hexamethyl-3H-indolium tetrafluoroborate,
1,2,3,3,4,7-hexamethyl-3H-indolium tetrafluoroborate,
5-fluoro-1,2,3,3-tetramethyl-3H-indolium iodide,
5-isopropyl-1,2,3,3-tetramethyl-3H-indolium iodide,
5-nitro-1,3,3-trimethyl-2-methyleneindoline
and especially
5-methoxy-1,2,3,3-tetramethyl-3H-indolium iodide,
5-methoxy-6-nitro-1,2,3,3-tetramethyl-3H-indolium chloride,
5-hydroxy-1,2,3,3-tetramethyl-3H-indolium iodide and
5-N-acetylamino-1,2,3,3-tetramethyl-3H-indolium acetate.
The compounds of formulas (I) and Ia) used according to the invention are known from the literature or can be prepared by standard methods of synthesis known from the literature, for example such as those described in the dissertation by Andreas Leiminer, University of Regensburg (1995); in the German Unexamined Patent Application [DE-OS] 1 949 716 or in U.S. Pat. No. 3,865,837. By the electrophilic substitution reactions known from the literature, additional, new substituents, for example a nitro function, can be introduced into the aromatic ring. In this respect, the reader is referred particularly to the synthesis method described by D. J. Gale and J. F. K. Wilshire in J. Soc. Dyers Colour; 1974. pp. 97-100. By later treatment with reducing or oxidizing agents or with the aid of appropriate protective group addition or elimination reactions, the functional nature of the introduced substituents can be modified whereby additional compounds of general formulas (I) and (Ia) can be obtained.
Suitable carbonyl compounds are, in particular, the following aldehydes: vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxybenzaldehyde), 3,4-dihydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-methyl-5-imidazolecarboxaldehyde, 4-dimethylaminocinnamaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4xe2x80x2-hydroxybiphenyl-1-carboxaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, indole-3-carboxaldehyde, benzene-1,4-dicarboxaldehyde, 4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquinone, 4-carboxybenzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 3-methoxy-4-(1-pyrrolidinyl)benzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 1,2,-phthalaldehyde, pyrrole-2-aldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde, chromone-3-carboxaldehyde, 6-methyl-4-oxo-1 (4H)-benzopyran-3-carboxaldehyde, N-methylpyrrole-2-aldehyde, 5-methylfufural, 6-hydroxychromene-3-carboxaldehyde, 6-methylindole-3-carboxaldehyde, 4-dibutylaminobenzaldehyde, N-ethyl-carbazole-3-aldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde, 5-[4-(diethylamino)phenyl]-2,4-pentadienal, 2,3-thiophenecarboxaldehyde, 2,5-thiophenedicarboxaldehyde, 2-methoxy-1-naphthaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde and 4-nitrobenzaldehyde.
The compounds of formulas (I) and (Ia) are kept separated from the carbonyl compounds until shortly before use. As a rule, the colorant of the invention is a mixture of the two components A1 and A2, namely of a dye carrier composition (A1) containing the compounds (I) and/or (Ia) and optionally a direct dye, and an additional dye carrier composition (A2) containing the carbonyl compound and optionally a direct dye. These two components are mixed just before use to give a ready-for-use colorant which is then applied to the fibers to be dyed. One or both components can, of course, also consist of several individual components which are mixed with each other just before use.
The compounds of formulas (I) and (Ia) and the carbonyl compounds are contained in each of the dye carrier compositions (component A1 or component A2) in a total amount from about 0.02 to 20 wt. % and preferably from 0.2 to 10 wt. %, and the ready-for-use colorant obtained by mixing components A1 and A2 contains the compounds of formulas (I) and (Ia) and the carbonyl compound in a total amount from about 0.01 to 10 wt. % and preferably from 0.1 to 5 wt. %.
Moreover, the coloring agent of the invention can optionally contain common physiologically tolerated direct dyes from the group of nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes.
The direct dyes can be contained in each of component A1 and component A2 in a total amount from about 0.2 to 10 wt. % and preferably from about 0.02 to 10 wt. %, the total amount of direct dyes in the ready-for-use colorant obtained by mixing components A1 and A2 being from about 0.01 to 10 wt. % and preferably from 0.1 to 5 wt. %.
The ready-for-use colorant and components A1 and A2 can be prepared in the form of, for example, a solution, particularly an aqueous or aqueous-alcoholic solution. Other suitable forms are creams, gels, aerosol foams or emulsions. The colorant composition is a mixture of the compounds of formulas ID (I) and (Ia) and/or a carbonyl compound with additives commonly used for such preparations.
Common additives used in colorants in the form of a solution, cream, emulsion, gel or aerosol foam are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, n-propanol and isopropanol, or polyols such as glycerol and 1,2-propanediol, moreover wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active agents, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty esters, furthermore thickeners such as higher fatty alcohols, starch or cellulose derivatives, perfumes, hair pretreatment agents, conditioners, hair swelling agents, preservatives, moreover vaselines, paraffin oils and fatty acids as well as hair-care agents, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The aforesaid components are used in amounts commonly employed for such purposes, for example the wetting agents and emulsifiers at a concentration of about 0.5 to 30 wt. % (based on the dye carrier composition), the thickeners in an amount of about 0.1 to 25 wt. % (based on the dye carrier composition) and the hair-care agents at a concentration of about 0.1 to 5.0 wt. % (based on the dye carrier composition).
As a rule, the pH of the ready-for-use colorant is about 3 to 11 and preferably 6 to 11, a pH of 6.5 to 8.5 being particularly preferred. The pH of the ready-for-use colorant obtained by mixing the enamine-containing component A1 with the carbonyl-containing component A2 depends on the pH of components A1 and A2 and on the mixing ratio of these two components. If necessary, after mixing components A1 and A2 the pH of the ready-for-use colorant can be adjusted to the desired value by adding an alkalinizing agent or an acid.
Suitable for adjusting the pH of the ready-for-use colorant and of components A1 and A2 are alkalinizing agents such as, for example, alkanolamines, alkylamines, alkali metal hydroxides or ammonium hydroxide, alkali metal carbonates or ammonium carbonate, or acids such as, for example, lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid, citric acid, ascorbic acid and boric acid.
The ready-for-use colorant is prepared immediately before use by mixing component A1 containing the compounds of formulas (I) and (Ia) with component A2 containing the carbonyl compound (optionally with addition of an alkalinizing agent or an acid) and is then applied to the fibers. Depending on the depth of shade, this mixture is allowed to act at a temperature from 20 to 50xc2x0 C., preferably from 30 to 40xc2x0 C., for 5 to 60 minutes and preferably for 15 to 30 minutes. The fibers are then rinsed with water and optionally washed with a shampoo.
The colorant of the invention permits gentle, uniform and lasting dyeing of the fibers, particularly keratin fibers, for example hair. Surprisingly, the resulting colorations can be removed at any time completely, quickly and gently by use of a reducing agent.
Another object of the present invention is therefore a multicomponent kit for dyeing and later decolorizing fibers, for example wool, silk, cotton or hair and particularly human hair, said kit being characterized in that it contains the dyeing agent (A) of the invention and a decolorizing component (B), said component B containing as the decolorizing agent at least one sulfite, for example ammonium sulfite, alkali metal sulfite or alkaline earth sulfite, and particularly sodium sulfite or ammonium sulfite.
The total amount of sulfites in component B is from about 0.1 to 10 wt. % and preferably from 2 to 5 wt. %.
The agent for decolorizing the fibers dyed with colorant A (in the following referred to as xe2x80x9cdecolorizerxe2x80x9d) can be in the form of an aqueous or aqueous-alcoholic solution, gel, cream, emulsion or foam, it being possible to package the decolorizer either in the form of a one-component preparation or in the form of a multicomponent preparation. The decolorizer can be packaged in the form of a powder or, to avoid dusting, in the form of tablets, including effervescent tablets, or as a granulate. Before use, the decolorizer is prepared with cold or warm water, optionally with addition of one or more of the auxiliary agents indicated in the following. It is also possible, however, for these auxiliary agents (if they are in a solid form) to be already contained in the decolorizing powder, decolorizing granulate or effervescent tablets. By wetting the powder with an oil or wax, dusting can be additionally reduced.
The decolorizer can also contain auxiliary agents, for example, a solvent such as water, a lower alcohol, for example ethanol, n-propanol, or isopropanol, a glycol ether or a polyol such as glycerol and, particularly 1,2-propanediol, furthermore a wetting agent or emulsifier from the classes of anionic, cationic, amphoteric or nonionic surface-active agents, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty esters, furthermore thickeners such as higher fatty alcohols, starch or cellulose derivatives, perfumes, hair pretreatment agents, conditioners, hair swelling agents, preservatives, vaselines, paraffin oils and fatty acids as well as hair-care agents, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine.
The pH of the decolorizer is from about 3 to 8 and particularly from 4 to 7. If necessary, the desired pH can be obtained by adjustment with a suitable acid, for example an xcex1-hydroxycarboxylic acid such as lactic acid, tartaric acid, citric acid or malic acid, or phosphoric acid, acetic acid, glycolic acid, salicylic acid, glutathione or gluconolactone, or with an alkalinizing agent such as an alkanolamine, alkylamine, alkali metal hydroxide, ammonium hydroxide, alkali metal carbonate, ammonium carbonate or alkali metal phosphate.
Depending on the color to be removed and the temperature (about 20 to 50xc2x0 C.), the exposure time to the decolorizer is from 5 to 60 minutes and particularly from 15 to 30 minutes. The decolorizing process can be accelerated by the action of heat. At the end of the exposure to the decolorizer, the hair is rinsed with water and optionally washed with a shampoo.
Although component B is well suited for decolorizing hair, particularly human hair, dyed with dye A, component B can in principle also be used for decolorizing other natural or man-made fibers dyed with colorant A, for example cotton, wool, silk, viscose, nylon and cellulose acetate.
The following examples will explain the object of the invention in greater detail without limiting its scope to the examples.